U.S. patent application number 16/492283 was filed with the patent office on 2019-12-26 for method for producing fluorinated hydrocarbons.
This patent application is currently assigned to ZEON CORPORATION. The applicant listed for this patent is ZEON CORPORATION. Invention is credited to Tatsuya SUGIMOTO.
Application Number | 20190389790 16/492283 |
Document ID | / |
Family ID | 63586422 |
Filed Date | 2019-12-26 |
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United States Patent
Application |
20190389790 |
Kind Code |
A1 |
SUGIMOTO; Tatsuya |
December 26, 2019 |
METHOD FOR PRODUCING FLUORINATED HYDROCARBONS
Abstract
Provided is a method for industrially advantageously producing a
fluorinated hydrocarbon (3). The disclosed method for producing a
fluorinated hydrocarbon represented by formula (3) includes
bringing into contact, in a hydrocarbon-based solvent, a secondary
or tertiary ether compound represented by formula (1) below with an
acid fluoride represented by formula (2) in the presence of lithium
salt or sodium salt (in the formulae, R.sup.1 and R.sup.2 each
represent a C.sub.1-3 alkyl, and R.sup.1 and R.sup.2 may be bonded
to each other to form a ring structure; R.sup.3 represents a
hydrogen atom, methyl, or ethyl; and R.sup.4 and R.sup.5 each
represent methyl or ethyl). ##STR00001##
Inventors: |
SUGIMOTO; Tatsuya;
(Chiyoda-ku, Tokyo, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
ZEON CORPORATION |
Chiyoda-ku Tokyo |
|
JP |
|
|
Assignee: |
ZEON CORPORATION
Chiyoda-ku Tokyo
JP
|
Family ID: |
63586422 |
Appl. No.: |
16/492283 |
Filed: |
March 13, 2018 |
PCT Filed: |
March 13, 2018 |
PCT NO: |
PCT/JP2018/009805 |
371 Date: |
September 9, 2019 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C07C 17/361 20130101;
C07C 17/16 20130101; C07C 41/16 20130101; B01J 21/02 20130101; B01J
27/12 20130101; B01J 23/04 20130101; C07C 19/08 20130101; C07C
51/60 20130101; C07C 41/16 20130101; C07C 43/04 20130101; C07C
51/60 20130101; C07C 53/42 20130101; C07C 51/60 20130101; C07C
53/40 20130101; C07C 17/16 20130101; C07C 19/08 20130101 |
International
Class: |
C07C 17/361 20060101
C07C017/361; C07C 19/08 20060101 C07C019/08 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 22, 2017 |
JP |
2017-056294 |
Claims
1. A method for producing a fluorinated hydrocarbon represented by
formula (3) below, wherein an ether compound represented by formula
(1) below and an acid fluoride represented by formula (2) below are
brought into contact with each other in a hydrocarbon-based
solvent, in the presence of lithium salt or sodium salt,
##STR00005## (in formula (1) above, R.sup.1 and R.sup.2 each
independently represent an alkyl group having 1 to 3 carbon atoms,
R.sup.3 represents a hydrogen atom, a methyl group or an ethyl
group, and R.sup.4 represents a methyl group or an ethyl group; and
R.sup.1 and R.sup.2 may be bonded to each other to form a cyclic
structure), R.sup.5--COF (2) (in formula (2) above, R.sup.5
represents a methyl group or an ethyl group), ##STR00006## (in
formula (3) above, R.sup.1 to R.sup.3 represent the same meanings
as described above).
2. The production method according to claim 1, wherein the lithium
salt or the sodium salt is inorganic acid salt.
3. The production method according to claim 1, wherein the ether
compound represented by the formula (1) is sec-butyl methyl ether
or t-butyl methyl ether.
4. The production method according to claim 1, wherein the acid
fluoride represented by the formula (2) is acetyl fluoride.
5. The production method according to claim 1, wherein the
fluorinated hydrocarbon represented by the formula (3) is
2-fluorobutane.
Description
TECHNICAL FIELD
[0001] Disclosed is a method for producing fluorinated hydrocarbons
useful as, for example: plasma reaction gases used in plasma
etching, plasma chemical vapor deposition (plasma CVD) and the
like; fluorine-containing medical intermediates; and
hydrofluorocarbon-based solvents. Highly purified fluorinated
hydrocarbons are suitable as plasma etching gases, plasma CVD gases
and the like, in particular, in the field of producing
semiconductor devices using plasma reaction.
BACKGROUND
[0002] Recently, miniaturization of semiconductor production
techniques has increasingly progressed, in such a way that the
state-of-the-art process has adopted generations having wiring
widths of the order of 20 nm and further 10 nm. Miniaturization
goes with the enhancement of the technical difficulty in the
miniaturization processing, and technical developments have been
progressed from various aspects of approach, with respect to the
materials, apparatuses, processing methods and others to be
used.
[0003] Under such circumstances, the present applicant has also
developed a dry etching gas capable of coping with the
state-of-the-art dry etching process, and has discovered that
saturated fluorinated hydrocarbons having small number of fluorine
atoms such as 2-fluorobutane have performances surpassing
monofluoromethane being used in etching of silicon nitride films
(see, for example, Patent Literature 1).
[0004] Several methods for producing 2-fluorobutane have hitherto
been known. For example, Patent Literature 2 describes a production
of 2-fluorobutane in a yield of 46%, by bringing
N,N'-diethyl-3-oxo-methyltrifluoropropylamine as a fluorinating
agent into contact with 2-butanol. Patent Literature 3 discloses
that the generation of fluorinated sec-butyl fluoride was confirmed
by bringing sulfur hexafluoride into contact with a sec-butyl
lithium solution in a cyclohexane/n-hexane mixed solvent. Patent
Literature 4 describes the preparation of 2-fluorobutane by
hydrogenation of 2-fluorobutadiene in the presence of a catalyst.
Non-Patent Literature 1 also discloses a method for preparing
monofluorinated hydrocarbons having a cyclic structure by acting
acetyl fluoride as a fluorinating agent to ether compounds having a
cyclic structure such as adamantyl methyl ether and cyclohexyl
methyl ether in the presence of a catalyst such as boron
trifluoride phosphoric acid complex or zinc fluoride.
CITATION LIST
Patent Literature
[0005] PTL 1: WO2009123038 [0006] PTL 2: JPS5946251A [0007] PTL 3:
JP2009292749A [0008] PTL 4: U.S. Pat. No. 2,550,953B
Non-Patent Literature
[0008] [0009] NPL 1: Bulletin of the Chemical Society of Japan,
Vol. 41, 1724 (1968)
SUMMARY
Technical Problem
[0010] As described above, several methods for producing
2-fluorobutane have hitherto been known.
[0011] However, the fluorinating agent used in the method described
in Patent Literature 2 is extremely high in price, and the method
described in Patent Literature 3 uses alkyl lithium, which involves
a risk of ignition. I tried a reaction in the absence of a solvent,
according to the description of Non-Patent Literature 1, and have
found that by-produced is a large amount of an acetic acid alkyl
ester, a by-product, in which the methyl group portion of a methyl
alkyl ether is substituted with an acetyl group derived from the
fluorinating agent.
[0012] As can be seen from the above, it has been difficult to
apply the conventional methods for producing 2-fluorobutane from
the viewpoint of the industrial productivity.
[0013] Under such circumstances as described above, I have
reported, in WO2015/122386, that a fluorinated hydrocarbons such as
2-fluorobutane is obtained in a good yield while the production of
acetic acid alkyl esters, by-products, is being suppressed, when an
alkyl ether compound of a secondary alcohol such as sec-butyl
methyl ether or sec-butyl ethyl ether is used as a starting
material, acetyl fluoride is used as a fluorinating agent, and an
ether complex of boron trifluoride is used as a catalyst, in a
hydrocarbon solvent.
[0014] However, a subsequent investigation has revealed that when a
fluorinated carbon such as 2-fluorobutane is brought into contact
with a Lewis acid compound (for example, boron trifluoride),
2-fluorobutane is partially decomposed into hydrogen fluoride and
olefins such as butenes, and thus it has been found that an
improvement is necessary. It has also been found that when an ether
complex of boron trifluoride is used, the ether compound
constituting the complex is liberated in the reaction system, the
liberated ether acts as an impurity for the fluorinated hydrocarbon
as the target compound, and the liberated ether sometimes causes a
load on the purification of the target compound, depending on the
type of the liberated ether. Further, boron trifluoride as a
catalyst needs to be readily separated from the reaction
liquid.
[0015] It could therefore be helpful to provide a method for
industrially advantageously producing a fluorinated hydrocarbon
such as 2-fluorobutane.
Solution to Problem
[0016] I have made a diligent study on the reaction between an
alkyl ether compound such as secondary or tertiary alcohol and
acetyl fluoride when both are brought into contact with each other
in a hydrocarbon-based solvent. As a result, I have discovered that
an industrially-inexpensive lithium salt or sodium salt may be
contained as a catalyst in a reaction system, so that: (a) no ether
compound (no impurity) is by-produced unlike when using an ether
complex of boron trifluoride as a catalyst, and thus a
substantially colorless reaction liquid is obtained; (b) the
catalyst residue is readily separated from the reaction liquid,
which thus allows for industrially advantageously producing the
targeted fluorinated hydrocarbon.
[0017] Thus, the following methods (i) to (v) for producing the
fluorinated hydrocarbon represented by formula (3) are
provided.
[0018] (i) A method for producing a fluorinated hydrocarbon
represented by formula (3) below, wherein an ether compound
represented by formula (1) and an acid fluoride represented by
formula (2) below are brought into contact with each other in a
hydrocarbon-based solvent, in the presence of lithium salt or
sodium salt,
##STR00002##
[0019] (in formula (1) above, R.sup.1 and R.sup.2 each
independently represent an alkyl group having 1 to 3 carbon atoms,
R.sup.3 represents a hydrogen atom, a methyl group or an ethyl
group, and R.sup.4 represents a methyl group or an ethyl group; and
R.sup.1 and R.sup.2 may be bonded to each other to form a cyclic
structure),
R.sup.5--COF (2)
[0020] (in formula (2) above, R.sup.5 represents a methyl group or
an ethyl group),
##STR00003##
[0021] (in formula (3) above, R.sup.1 to R.sup.3 represent the same
meanings as described above).
[0022] (ii) The production method according to (i), wherein the
lithium salt or the sodium salt is inorganic acid salt.
[0023] (iii) The production method according to (i) or (ii),
wherein an ether compound represented by formula (1) above is
sec-butyl methyl ether or t-butyl methyl ether.
[0024] (iv) The production method according to any one of (i) to
(iii), wherein the acid fluoride represented by formula (2) is
acetyl fluoride.
[0025] (v) The production method according to any one of (i) to
(iv), wherein the fluorinated hydrocarbon represented by formula
(3) is 2-fluorobutane.
Advantageous Effect
[0026] In the disclosed method, an industrially-inexpensive lithium
salt or sodium salt may be contained as a catalyst in the reaction
system, so that: no ether compound (impurities) is by-produced
unlike when using an ether complex of boron trifluoride as a
catalyst; and further, the catalyst residue is readily separated
from the reaction liquid in the post-treatment step, to thereby
obtain a substantially colorless reaction liquid, which thus allows
for industrially advantageously producing the targeted fluorinated
hydrocarbon.
DETAILED DESCRIPTION
[0027] Hereinafter, the disclosed method is described in
detail.
[0028] The disclosed method is for producing a fluorinated
hydrocarbon represented by formula (3) below (which may be
hereinafter referred to as "fluorinated hydrocarbon (3)"), by
bringing into contact an ether compound represented by formula (1)
below (which may be hereinafter referred to as "ether compound
(1)") with an acid fluoride represented by formula (2) (which may
be hereinafter referred to as "acid fluoride (2)"), in a
hydrocarbon-based solvent, in the presence of lithium salt or
sodium salt.
##STR00004##
[0029] [Ether Compound (1)]
[0030] The starting material used in the disclosed method is an
ether compound (1).
[0031] In formula (1), R.sup.1 and R.sup.2 each independently
represent an alkyl group having 1 to 3 carbon atoms.
[0032] Examples of the alkyl groups having 1 to 3 carbon atoms
represented by R.sup.1 and R.sup.2 may include: a methyl group, an
ethyl group, an n-propyl group, and an isopropyl group.
[0033] R.sup.1 and R.sup.2, which may be bonded to each other to
form a cyclic structure, are preferably not forming a cyclic
structure.
[0034] Examples of the cyclic structure formed by R.sup.1 and
R.sup.2 which are bonded to each other, together with carbon atoms
to which R.sup.1 and R.sup.2 are boded, include: a cyclopropane
ring; a cyclobutane ring; a cyclopentane ring; a cyclohexane ring;
and a cycloheptane ring.
[0035] R.sup.3 represents a hydrogen atom, a methyl group or an
ethyl group.
[0036] R.sup.4 represents a methyl group or an ethyl group.
[0037] Preferred examples of the ether compound (1) are those
having preferably 4 to 7 carbon atoms, more preferably 4 or 5
carbon atoms in total in R.sup.1 to R.sup.3.
[0038] Specific examples of the ether compound (1) include: methyl
ethers such as sec-butyl methyl ether, t-butyl methyl ether,
cyclobutyl methyl ether, 2-pentyl methyl ether, 3-pentyl methyl
ether, 2-methyl-2-butyl methyl ether, and cyclopentyl methyl ether;
and ethyl ethers such as sec-butyl ethyl ether, t-butyl ethyl
ether, cyclobutyl ethyl ether, 2-pentyl ethyl ether, 3-pentyl ethyl
ether, 2-methyl-2-butyl ethyl ether, and cyclopentyl ethyl
ether.
[0039] Of these, alkyl methyl ether compounds having 4 or 5 carbon
atoms, such as: sec-butyl methyl ether, t-butyl methyl ether,
2-pentyl methyl ether; and alkyl ethyl ether compounds having 4 or
5 carbon atoms, such as: sec-butyl ethyl ether, t-butyl ethyl
ether, and 2-pentyl ethyl ether are preferred in terms of efficient
production of the target product and easy availability of the raw
materials, with sec-butyl methyl ether, sec-butyl ethyl ether,
t-butyl methyl ether, 2-pentyl methyl ether being further
preferred, and sec-butyl methyl ether, t-butyl methyl ether being
still further preferred, in terms of efficient production of the
target product.
[0040] Examples of the method for producing the ether compound (1)
include, without being particularly limited to: heretofore known
methods such as a method described in Journal of Japan Oil
Chemists' Society (Yukagaku), Vol. 31, p. 960 (1982), and a method
described in Journal of American Chemical Society, Vol. 54, 2088
(1932) may be employed. In the former method, the corresponding
alcohol is brought into contact with a sulfuric acid ester in the
presence of a phase-transfer catalyst such as a 50% concentration
of sodium hydroxide and tetraalkylammonium salt. In the latter
method, the corresponding anhydrous alcohol is brought into contact
with metallic sodium, and then brought into contact with an alkyl
bromide or an alkyl iodide to produce an ether compound.
[0041] [Acid Fluoride (2)]
[0042] The disclosed method uses the acid fluoride (2) as a
fluorinating agent.
[0043] In formula (2), R.sup.5 is a methyl group or an ethyl
group.
[0044] The acid fluoride (2) is specifically acetyl fluoride or
propionyl fluoride, with acetyl fluoride being preferred in terms
of efficient production of the target product.
[0045] The acid fluoride (2) is a heretofore known substance, can
be produced by a heretofore known method, and is available. The
acid fluoride (2) can be produced according to the method described
in, for example, "Journal of Chemical Society Dalton Transaction,
2129 (1975)", or "Journal of American Chemical Society, Vol. 59,
1474 (1937)". In the former method, potassium fluoride is dissolved
in acetic acid, acetyl chloride or propionyl chloride is added
under heating, and generated acetyl fluoride or propionyl fluoride
is collected. In the latter method, sodium hydrogen difluoride is
dissolved in acetic anhydride, acetyl chloride is added, and the
generated acetyl fluoride is collected.
[0046] The amount of the acid fluoride (2) used is generally 7
equivalents or more, preferably 0.8 equivalents or more, more
preferably 0.9 equivalents or more, and generally 3.0 equivalents
or less, preferably 2.5 equivalents or less, more preferably 2.0
equivalents or less, in relation to 1 equivalent of the ether
compound (1). When the amount of the acid fluoride (2) used falls
within such a range, the productivity is excellent, and the
post-treatment or the purification process is not cumbersome, which
is preferable.
[0047] Of the acid fluorides (2), acetyl fluoride acts as a
fluorinating agent and then is converted into methyl acetate, when
a methyl ether compound is used as the ether compound (1). Acetyl
fluoride is converted into ethyl acetate when an ethyl ether
compound is used as the ether compound (1).
[0048] Of the acid fluorides (2), propionyl fluoride acts as a
fluorinating agent and then is converted into methyl propionate,
when a methyl ether compound is used as the ether compound (1).
Propionyl fluoride is converted into ethyl propionate when an ethyl
ether compound is used as the ether compound (1).
[0049] [Lithium Salt/Sodium Salt]
[0050] In the disclosed method, the ether compound (1) is brought
into contact with the acid fluoride (2), in the presence of lithium
salt or sodium salt.
[0051] Specific examples of the lithium salt include: inorganic
acid lithium salt such as lithium fluoride, lithium chloride,
lithium bromide, lithium iodide, lithium phosphate, lithium
nitrate, lithium tetrafluoroborate, lithium carbonate, lithium
sulfate, lithium hexafluorophosphate, lithium sulphamate; and
organic acid lithium salt such as lithium formate, lithium acetate,
lithium oxalate, lithium methanesulfonate, lithium
p-toluenesulfonate, lithium trifluoroacetate, lithium maleate,
lithium fumarate, lithium itaconate, lithium
trifluoromethanesulfonate, lithium nonafluorobutansulfonate.
[0052] Specific examples of the sodium salt include: inorganic acid
sodium salt such as sodium fluoride, sodium chloride, sodium
bromide, sodium iodide, sodium phosphate, sodium nitrate, sodium
tetrafluoroborate, sodium carbonate, sodium sulfate, sodium
hexafluorophosphate, sodium hydrogencarbonate, sodium hydrogen
sulfite, sodium sulfite, sodium thiosulfate, sodium hydrogen
difluoride, sodium sulphamate; and organic acid sodium salt such as
sodium formate, sodium acetate, sodium oxalate, sodium
methanesulfonate, sodium p-toluenesulfonate, sodium
trifluoroacetate, sodium heptafluorobutyrate, sodium maleate,
sodium fumarate, sodium itaconate, sodium
trifluoromethanesulfonate, sodium nonafluorobutansulfonate.
[0053] These lithium salts and sodium salts may each be used alone
or in combination of two or more kinds.
[0054] Of these, inorganic acid lithium salt such as lithium
fluoride, lithium chloride, lithium bromide, lithium iodide,
lithium phosphate, lithium nitrate, lithium tetrafluoroborate,
lithium carbonate, lithium sulfate, lithium hexafluorophosphate,
lithium sulphamate; and inorganic acid sodium salt such as sodium
fluoride, sodium chloride, sodium bromide, sodium iodide, sodium
phosphate, sodium nitrate, sodium tetrafluoroborate, sodium
carbonate, sodium sulfate, sodium hexafluorophosphate, sodium
hydrogencarbonate, sodium hydrogensulfite, sodium sulfite, sodium
thiosulfate, sodium hydrogen difluoride, sodium sulphamate are
preferred in terms of more readily obtaining the effect of the
disclosure, with lithium fluoride, with lithium chloride, lithium
bromide, lithium iodide, lithium phosphate, lithium nitrate,
lithium tetrafluoroborate, lithium carbonate, sodium fluoride,
sodium chloride, sodium bromide, sodium iodide, sodium phosphate,
sodium nitrate, sodium tetrafluoroborate, sodium carbonate, sodium
sulfate, sodium hexafluorophosphate, sodium hydrogencarbonate being
more preferred in terms of economy, availability, and efficient
production of the target product.
[0055] The amount of lithium salt or sodium salt used is preferably
0.005 equivalents or more, more preferably 0.01 equivalent or more,
and preferably 0.3 equivalent or less, more preferably 0.2
equivalents or less, in terms of the lithium content in the lithium
salt (or the sodium content in the sodium salt), in relation to 1
equivalent of the ether compound (1) as the raw material.
[0056] When the amount of the lithium salt or the sodium salt is
too small, the reaction fails to complete, which may leave residue
of the ether compound (1) as the raw material. When the lithium
salt or the sodium salt is added too much, which is economically
disadvantageous, the solid concentration of the content is
increased, making the stirring difficult and potentially causing
some troubles, for example, in post-treatment.
[0057] [Hydrocarbon-Based Solvent]
[0058] The disclosed method uses a hydrocarbon-based solvent as a
reaction solvent. The use of a hydrocarbon-based solvent as a
reaction solvent provides excellent effects as disclosed herein.
Without any solvent, lithium salt or sodium salt as the catalyst
are brought into excessive contact with the ether compound (1) as
the raw material or with the generated fluorinated hydrocarbon (3)
as the target, which may potentially result in increased generation
of byproducts such as olefin.
[0059] As the hydrocarbon-based solvent used in the disclosed
method, in consideration of the load to be applied in the
purification process (distillation purification), preferably used
is a compound having a boiling point higher by 25.degree. C. or
more than the boiling point of the fluorinated hydrocarbon (3) as
the product.
[0060] Specific examples of such a hydrocarbon-based solvent
include: hydrocarbon-based solvents having 5 carbon atoms such as
n-pentane and cyclopentane; hydrocarbon-based solvents having 6
carbon atoms such as n-hexane, 2-methylpentane, 3-methylpentane,
2,2-dimethylbutane, 2,3-dimethylbutane, cyclohexane and
methylcyclopentane; hydrocarbon-based solvents having 7 carbon
atoms such as n-heptane, 2-methylhexane, 3-methylhexane,
2,2-dimethylpentane, 2,3-dimethylpentane, 2,4-dimethylpentane,
3,3-dimethylpentane, 3-ethylpentane, 2,2,3-trimethylbutane,
methylcyclohexane, cycloheptane and toluene; hydrocarbon-based
solvents having 8 carbon atoms such as n-octane, 4-methylheptane,
2-methylheptane, 3-methylheptane, 2,2-dimethylhexane,
2,3-dimethylhexane, 2,4-dimethylhexane, 2,5-dimethylhexane,
3,3-dimethylhexane, 3,4-dimethylhexane, 3-ethylhexane,
2,2,3-trimethylpentane, 2,2,4-trimethylpentane, 2,3,3-trim ethyl
pentane, 2,3,4-trimethylpentane, 2-methyl-3-ethylpentane,
3-methyl-3-ethylpentane, cyclooctane, ethyl benzene and xylene.
When the hydrocarbon-based solvents are mutually in a relationship
of being isomers, a mixture of composed such isomers may also be
used as a hydrocarbon-based solvent.
[0061] From the viewpoint of easiness in handling, more preferable
among these are: hydrocarbon-based solvents having 6 carbon atoms
such as n-hexane, 2-methylpentane, 3-methylpentane,
2,2-dimethylbutane, 2,3-dimethylbutane, cyclohexane and
methylcyclopentane; and hydrocarbon-based solvents having 7 carbon
atoms such as n-heptane, 2-methylhexane, 3-methylhexane,
2,2-dimethylpentane, 2,3-dimethylpentane, 2,4-dimethylpentane,
3,3-dimethylpentane, 3-ethylpentane, 2,2,3-trimethylbutane,
methylcyclohexane, cycloheptane and toluene.
[0062] The amount of each of these hydrocarbon-based solvents used
is generally 1 ml or more, preferably 2 ml or more, more preferably
2.5 ml or more, and generally 10 ml or less, preferably 5 ml or
less, and more preferably 3 ml or less, in relation to 1 g of the
ether compound (1) to be the raw material. When the amount of the
hydrocarbon-based solvent used is too small, the amount of the
acetic acid alkyl ester produced as a by-product is increased. On
the other hand, when the amount of the hydrocarbon-based solvent
used is too large, a long period of time may be required to
complete the reaction, or the treatment of the waste liquid during
post-treatment may be cumbersome.
[0063] [Reaction]
[0064] An exemplary method of bringing the ether compound (1) into
contact with the acid fluoride (2) may include: charging, in a
reactor, the ether compound (1) as the raw material and a
hydrocarbon-based solvent; cooling the reactor to a predetermined
temperature (of, for example, 0.degree. C. or higher and 10.degree.
C. or lower) and then adding the acid fluoride (2) as a
fluorinating agent, and further adding lithium salt or sodium salt
as a catalyst; and thereafter keeping stirring the content while
holding the content at a predetermined temperature.
[0065] The lithium salt or the sodium salt as a catalyst may be
added all at once, or divided in batches to be added a plurality of
times such as twice or three times.
[0066] The temperature (reaction temperature) at which the ether
compound (1) and the acid fluoride (2) are brought into contact
with each other is preferably 0.degree. C. or higher, more
preferably 10.degree. C. or higher, and preferably 40.degree. C. or
lower, more preferably 30.degree. C. or lower. The aforementioned
temperature range allows for properly regulating the reaction rate
while achieving excellent productivity, and suppressing
volatilization loss of the produced fluorinated hydrocarbon
(3).
[0067] The reaction time depends on the combination of the ether
compound (1) to be the raw material, the acid fluoride (2) and the
hydrocarbon-based solvent or on the reaction scale, but is
generally 3 hours or longer and 24 hours or shorter, preferably 5
hours or longer and 20 hours or shorter, and more preferably 5
hours or longer and 12 hours or shorter.
[0068] When the reaction time is too short, the reaction is not
completed, leaving unreacted raw materials or the acid fluoride (2)
functioning as the fluorinating agent remain in a large amount,
which may make the post-treatment cumbersome. On the other hand,
when the reaction time is too long, some troubles are likely to be
caused in which the reaction may excessively occur, increasing the
production amount of the alkyl ester as a by-product.
[0069] After the completion of reaction, the reaction liquid most
likely contains catalyst residue that has settled therein. The
reaction liquid may be filtered to separate lithium fluoride (or
sodium fluoride) along with catalyst residue, to thereby recover
the reaction liquid. Further, in order to remove a trace amount of
fluorinated hydrogen generated in a reaction, a reaction reagent
(hydrogen fluoride remover) for removing hydrogen fluoride such as
sodium fluoride may preferably be added to the reaction liquid and
stirred, before filtering the reaction liquid.
[0070] The disclosed method uses a solid catalyst (lithium salt or
sodium salt), which allows for readily separating and removing the
catalyst through filtration without needing any troublesome
operation such as neutralization.
[0071] Thereafter, the filtrate thus obtained may be distilled by
means of a distillation column, to thereby isolate the fluorinated
hydrocarbon (3) as the target product.
[0072] When the fluorinated hydrocarbon (3) is desired to have
still higher purity, a rectification may be again performed.
[0073] In the manner as described above, the fluorinated
hydrocarbon (3) can be obtained.
[0074] According to the disclosed method, the reaction system
includes, as a catalyst, industrially-inexpensive lithium salt or
sodium salt, and thus no ether compound (impurity) is by-produced
unlike when using an ether complex of boron trifluoride as a
catalyst, and a substantially colorless reaction liquid can be
obtained. Further, the catalyst residue is readily separated from
the reaction liquid, which allows for industrially advantageously
producing the targeted fluorinated hydrocarbon.
[0075] Specific examples of the fluorinated hydrocarbon (3)
obtained by the production method of the present invention include:
2-fluorobutane, t-butyl fluoride, 2-fluoropentane, 3-fluoropentane,
2-methyl-2-fluorobutane, cyclobutyl fluoride, cyclopentyl fluoride
and cyclohexyl fluoride, Of these, 2-fluorobutane, 2-fluoropentane,
and 2-fluoro-2-methylpropane are preferred, with 2-fluorobutane
being particularly preferred, in terms of the easy availability of
the raw materials.
EXAMPLES
[0076] Hereinafter, by way of Examples, the present invention is
described in further details, but the scope of the present
invention is not limited by following Examples. Note that "%"
represents "mass %" unless otherwise specified.
[0077] The analytical conditions adopted hereinafter are as
follows.
[0078] Gas Chromatography Analysis (GC Analysis)
[0079] Apparatus: HP-6890 (manufactured by Agilent Technologies,
Inc.)
[0080] Column: Inert Cap-1 (manufactured by GL Sciences Inc.,
length: 60 m, inner diameter: 0.25 mm, film thickness: 1.5
.mu.m)
[0081] Column temperature: Maintained at 40.degree. C. for 10
minutes, subsequently, increased to 240.degree. C. at a rate of
20.degree. C./min., and then maintained at 240.degree. C. for 10
minutes
[0082] Injection temperature: 200.degree. C.
[0083] Carrier gas: Nitrogen
[0084] Split ratio: 100/1
[0085] Detector: FID
[0086] Gas Chromatography Mass Analysis (GC-MS)
[0087] GC section: HP-6890 (manufactured by Agilent Technologies,
Inc.)
[0088] Column: Inert Cap-1 (manufactured by GL Sciences Inc.,
length: 60 m, inner diameter: 0.25 mm, film thickness: 1.5
.mu.m)
[0089] Column temperature: Maintained at 40.degree. C. for 10
minutes, subsequently, increased to 240.degree. C. at a rate of
20.degree. C./min., and then maintained at 240.degree. C. for 10
minutes
[0090] MS section: 5973 NETWORK (manufactured by Agilent
Technologies, Inc.)
[0091] Detector: EI-type (acceleration voltage: 70 eV)
[Production Example 1] Production of sec-Butyl Methyl Ether
[0092] In a 500 mL volume eggplant flask with a stirring bar placed
therein, 360 mL of 2-butanol and 37.3 g of flaky potassium
hydroxide (manufactured by Aldrich Corporation, purity:
approximately 90%) were charged, and the resulting mixture was
stirred for approximately 2.5 hours at 50.degree. C. When potassium
hydroxide was dissolved to produce a uniform solution, the heating
was once ceased. To the resulting uniform solution, 84.4 g of
iodomethane was added, and the resulting mixture was stirred at
50.degree. C. for a little over 3 hours in a state of being
equipped with a Dimroth condenser. After the completion of the
reaction, the reaction liquid was cooled to room temperature
(approximately 25.degree. C.; hereinafter the same) and the
supernatant solution was analyzed by gas chromatography (which may
be hereinafter referred to as "GC"), to find that iodomethane was
virtually consumed, and the supernatant solution contained
2-butanol and sec-butyl methyl ether as the target.
[0093] Potassium iodide was filtered off from the content in the
eggplant flask, to obtain a filtrate. The filtered-off potassium
iodide was dissolved in a small amount of water to separate the
upper layer of an organic phase, and the separated organic phase
was mixed with the foregoing filtrate, to thereby obtain a filtrate
mixture.
[0094] The obtained filtrate mixture was charged in a distillation
still, and distilled by using a KS-type rectifier (manufactured by
TOKA SEIKI Co., Ltd., column length: 30 cm, column packing
material: Helipack No. 1). The fraction of the column top
temperature of 55-56.degree. C. was collected, the water
azeotropically boiled and distilled was separated by using a
separating funnel, the obtained distillate was dried with the
molecular sieves 4A, and thus 38 g of sec-butyl methyl ether was
obtained (yield: 72%).
GC-MS (EI-MS): m/z 73, 59, 41, 29
[Production Example 2] Production of sec-Butyl Ethyl Ether
[0095] In a 500 mL volume eggplant flask with a stirring bar placed
therein, 240 mL of 2-butanol and 24.8 g of flaky potassium
hydroxide (manufactured by Aldrich Corporation, purity:
approximately 90%) were charged, and the resulting mixture was
stirred for 3 hours at 50.degree. C. When potassium hydroxide was
dissolved to produce a uniform solution, the heating was once
ceased. To the resulting uniform solution, 43 g of ethyl bromide
was added, and the mixture was stirred at 70.degree. C. for a
little over 4 hours in a state of being equipped with a Dimroth
condenser. The reaction mixture was cooled to room temperature and
the supernatant solution was analyzed by GC, to find that ethyl
bromide was virtually consumed, and the supernatant solution
contained 2-butanol and sec-butyl ethyl ether as the target.
[0096] Potassium bromide was filtered off from the content in the
eggplant flask, to obtain a filtrate. The filtered-off potassium
bromide was dissolved in a small amount of water, the upper layer
of an organic phase was separated, and the separated organic phase
was mixed with the foregoing filtrate mixture to obtain a filtrate
mixture.
[0097] The obtained filtrate mixture was charged in a distillation
still, and distilled by using a KS-type rectifier (manufactured by
TOKA SEIKI Co., Ltd., column length: 30 cm, column packing
material: Helipack No. 1). The fraction of the column top
temperature of 68-69.degree. C. was collected, the water
azeotropically boiled and distilled was separated by using a
separating funnel, the obtained distillate was dried with the
molecular sieves 4A, and thus 31 g of sec-butyl ethyl ether was
obtained (yield: 51%).
GC-MS (EI-MS): m/z 87, 73, 59, 45
[Production Example 3] Production of 2-Pentyl Methyl Ether
[0098] In a 500 mL volume eggplant flask equipped with a Dimroth
condenser, a dropping funnel and a stirring bar, 300 mL of
2-pentanol and 30 g of potassium hydroxide (manufactured by Wako
Pure Chemical Industries, Ltd., purity: approximately 85%) were
charged, and the resulting mixture was stirred for approximately
2.5 hours at 50.degree. C. When potassium hydroxide was dissolved
to produce a uniform solution, 81 g of methyl p-toluenesulfonate
was added from a dropping funnel to the uniform solution over
approximately 1 hour, and the resulting mixture was stirred at
50.degree. C. for a little over 3 hours. The reaction mixture was
cooled to room temperature, and the content was transferred into a
beaker; water was added to the beaker, and thus the produced
potassium p-toluenesulfonate was dissolved. The solution in the
beaker was transferred into a separating funnel, the aqueous layer
was separated, and thus a liquid mixture composed of 2-pentyl
methyl ether and 2-pentanol was obtained.
[0099] The obtained liquid mixture was charged in a distillation
still, and distilled by using a KS-type rectifier (manufactured by
TOKA SEIKI Co., Ltd., column length: 30 cm, column packing
material: Helipack No. 1). The fraction of the column top
temperature of 74-75.degree. C. was collected, the water
azeotropically boiled and distilled was separated by using a
separating funnel, the obtained distillate was dried with the
molecular sieves 4A, and thus 16 g of 2-pentyl methyl ether was
obtained (yield: 37%).
GC-MS (EI-MS): m/z 87, 71, 59, 45
[Production Example 4] Production of Acetyl Fluoride
[0100] In a 500 mL volume glass reactor equipped with a stirrer, a
dropping funnel and a collection trap, 200 mL of acetic anhydride
and 46.9 g of potassium hydrogen difluoride were charged, and the
resulting mixture was stirred while being heated to 40.degree. C.
To the mixture, 47 g of acetyl chloride was dropwise added from the
dropping funnel over 40 minutes, and after the completion of the
dropwise addition, the temperature of the reactor was increased by
10.degree. C. every 15 minutes. The reactor was finally heated to
90.degree. C., and then maintained at that temperature for 20
minutes, and subsequently the reaction was terminated. Acetyl
fluoride distilled from the reactor during the reaction was
collected in a glass trap cooled with ice water. The crude product
amount was 47.6 g (crude yield: 128%). In the present reaction,
acetyl fluoride is also produced from acetic anhydride, and
accordingly the yield exceeds 100%.
[0101] The obtained crude acetyl fluoride was subjected to a simple
distillation, the fraction of the column top temperature of
20-24.degree. C. was collected, and thus 42.4 g of acetyl fluoride
was obtained (yield: 114%).
[Production Example 5] Production of Propionyl Fluoride
[0102] In a 500 mL volume glass reactor equipped with a stirrer, a
dropping funnel and a collection trap, 200 mL of propionic
anhydride and 46.8 g of potassium hydrogen difluoride were charged,
and the resulting mixture was stirred while being heated to
90.degree. C. To the mixture, 55.5 g of propionyl chloride was
dropwise added from the dropping funnel over 1 hour, and after the
completion of the dropwise addition, the mixture was further
stirred for 15 minutes. Subsequently, the temperature of the
reactor was increased by 10.degree. C. every 15 minutes, so as to
heat the reactor up to 110.degree. C. The resulting mixture was
stirred at 110.degree. C. for 30 minutes, and then the reaction was
terminated. Propionyl fluoride distilled from the reactor during
the reaction was collected in a glass trap cooled with ice water.
The crude yield was 132%. In the present reaction, propionyl
fluoride is also produced from propionic anhydride, and accordingly
the yield exceeds 100%.
[0103] The obtained crude propionyl fluoride was subjected to a
simple distillation, the fraction of the column top temperature of
42-43.degree. C. was collected, and thus 46.8 g of propionyl
fluoride was obtained (yield: 103%).
Example 1
[0104] In a 50 mL volume glass reactor equipped with a stirring bar
and a Dimroth condenser (circulating a coolant of 0.degree. C.),
1.76 g of sec-butyl methyl ether synthesized in Production Example
1 and 5 mL of dry n-hexane were charged, under nitrogen atmosphere,
and the resulting mixture was cooled to 0.degree. C. To the cooled
mixture, 2.48 g of acetyl fluoride synthesized in Production
Example 4 was added, and the resulting mixture was stirred and
further added with 0.094 g of lithium tetrafluoroborate
(manufactured by Wako Pure Chemical Industries, Ltd.). The mixture
was stirred at 0.degree. C. for 30 minutes and then the temperature
was increased to 20.degree. C., and the content was stirred for
another 6.5 hours. After the stirring was stopped, the mixture was
left to stand, so as to obtain a gray precipitate and a colorless
solution.
[0105] After the completion of the reaction, the reaction mixture
was analyzed by GC, and consequently it was found that sec-butyl
methyl ether, the raw material, was substantially disappeared,
2-fluorobutane, the target compound, was produced in 8.87 area %,
and 1-butene, (E)-2-butene, and (Z)-2-butene were produced in 0.14
area %, 4.22 area %, and 2.71 area %, respectively. In addition,
2-acetoxybutane (raw material derived component) attributable to
the acetoxylation of the raw material was produced in 3.84 area %.
The remainder was composed of n-hexane, the solvent, and methyl
acetate resulting from the reaction.
[0106] The reaction liquid was filtered through a PTFE membrane
filter (pore size: 0.2 .mu.m) so as to remove precipitate (catalyst
residue), to thereby recover a colorless transparent solution.
Example 2
[0107] A reaction was performed in the same manner as in Example 1,
except that 0.094 g of lithium tetrafluoroborate as the catalyst
was replaced with 0.028 g of lithium fluoride. After the completion
of the reaction, the reaction mixture was analyzed by GC, and
consequently it was found that sec-butyl methyl ether, the raw
material, was substantially disappeared, 2-fluorobutane, the target
compound, was produced in 16.73 area %, and 1-butene, (E)-2-butane,
and (Z)-2-butane were produced in 0.12 area %, 4.69 area %, and
1.96 area %, respectively. In addition, 2-acetoxybutane
attributable to the acetoxylation of the raw material was produced
in 2.00 area %. The remainder was composed of n-hexane, the
solvent, and methyl acetate resulting from the reaction.
Examples 3-5
[0108] A reaction was performed in the same manner as in Example 1,
except that 0.094 g of lithium tetrafluoroborate as the catalyst
was replaced with: 0.046 g of lithium chloride; 0.088 g of lithium
bromide; and 0.136 g of lithium iodide, respectively. When lithium
bromide or lithium iodide was used, 2-bromobutane and 2-iodobutane
as halogen exchangers were by-produced in 0.15 area % and 1.18 area
%, respectively, in addition to 2-acetoxybutane attributable to the
acetoxylation of the raw material. The reaction results are
summarized in Table 1.
Example 6
[0109] A reaction was performed in the same manner as in Example 1,
except that 0.094 g of lithium tetrafluoroborate as the catalyst
was replaced with 0.069 g of lithium nitrate, and further the
stirring time at 20.degree. C. was changed from 6.5 hours to 7
hours. After the completion of the reaction, the reaction mixture
was analyzed by GC, and consequently it was found that sec-butyl
methyl ether, the raw material, was produced in 1.41 area %,
2-fluorobutane, the target compound, was produced in 15.03 area %,
and 1-butene, (E)-2-butene, and (Z)-2-butene were produced in 0.11
area %, 4.40 area %, and 1.77 area %, respectively. In addition,
2-acetoxybutane attributable to the acetoxylation of the raw
material was produced in 2.36 area %. The remainder was composed of
n-hexane, the solvent, and methyl acetate resulting from the
reaction.
Examples 7-9
[0110] A reaction was performed in the same manner as in Example 1,
except that 0.094 g of lithium tetrafluoroborate as the catalyst
was replaced with: 0.037 g of lithium carbonate; 0.039 g of lithium
phosphate; and 0.103 g of lithium sulfamate, respectively. The
reaction results are summarized in Table 1.
Examples 10-14, and 16
[0111] A reaction was performed in the same manner as in Example 1,
except that 0.094 g of lithium tetrafluoroborate as the catalyst
was replaced with: 0.066 g of lithium acetate; 0.064 g of lithium
maleate; 0.051 g of lithium oxalate; 0.102 g of lithium
methanesulfonate; 0.178 g of lithium p-toluene sulfonate; and 0.306
g of lithium nonafluorobutanesulfonate, respectively. The reaction
results are summarized in Table 1.
Example 15
[0112] A reaction was performed in the same manner as in Example 1,
except that 0.094 g of lithium tetrafluoroborate as the catalyst
was replaced with 0.156 g of lithium trifluoromethanesulfonate, and
further the stirring time at 20.degree. C. was changed to 7.5
hours. After the completion of the reaction, the reaction mixture
was analyzed by GC, and consequently it was found that sec-butyl
methyl ether, the raw material, was produced in 2.09 area %,
2-fluorobutane, the target compound, was produced in 10.76 area %,
and 1-butene, (E)-2-butene, and (Z)-2-butene were produced in 0.28
area %, 7.54 area %, and 3.29 area %, respectively. In addition,
2-acetoxybutane attributable to the acetoxylation of the raw
material was produced in 2.61 area %. The remainder was composed of
n-hexane, the solvent, and methyl acetate resulting from the
reaction.
Example 17
[0113] In a 50 mL volume glass reactor equipped with a Dimroth
condenser (circulating a coolant of 0.degree. C.), 1.76 g of
sec-butyl methyl ether synthesized in Production Example 1 and 5 mL
of dry n-hexane were charged, under nitrogen atmosphere, and the
resulting mixture was cooled to 0.degree. C. To the cooled mixture,
2.48 g of acetyl fluoride synthesized in Production Example 4 was
added, and the resulting mixture was stirred and further added with
0.11 g of sodium tetrafluoroborate (manufactured by Wako Pure
Chemical Industries, Ltd.). The mixture was stirred at 0.degree. C.
for 30 minutes and then the temperature was increased to 20.degree.
C., and the content was stirred for another 6.5 hours. After the
stirring was stopped, the mixture was left to stand, so as to
obtain a gray precipitate and a colorless solution.
[0114] After the completion of the reaction, the reaction mixture
was analyzed by GC, and consequently it was found that sec-butyl
methyl ether, the raw material, was substantially disappeared,
2-fluorobutane, the target compound, was produced in 12.61 area %,
and 1-butene, (E)-2-butene, and (Z)-2-butene were produced in 0.13
area %, 5.62 area %, and 1.95 area %, respectively. In addition,
2-acetoxybutane (raw material derived component) attributable to
the acetoxylation of the raw material was produced in 2.25 area %.
The remainder was composed of n-hexane, the solvent, and methyl
acetate resulting from the reaction.
[0115] The reaction liquid is filtered by PTFE membrane filter
(pore size: 0.2 .mu.m) so as to remove precipitate (catalyst
residue), to thereby recover a colorless transparent solution.
Examples 18-19
[0116] A reaction was performed in the same manner as in Example
17, except that 0.11 g of sodium tetrafluoroborate as the catalyst
was replaced with: 0.042 g of sodium fluoride; and 0.102 g of
sodium bromide, respectively. The reaction results are summarized
in Table 1.
Example 20
[0117] A reaction was performed in the same manner as in Example
17, except that 0.11 g of sodium tetrafluoroborate as the catalyst
was replaced with 0.15 g of sodium iodide, and further the stirring
time at 20.degree. C. was changed to 5.5 hours. After the
completion of the reaction, the reaction mixture was analyzed by
GC, and consequently it was found that that sec-butyl methyl ether,
the raw material, was substantially disappeared, 2-fluorobutane,
the target compound, was produced in 13.34 area %, and 1-butene,
(E)-2-butene, and (Z)-2-butene were produced in 0.21 area %, 5.72
area %, and 2.29 area %, respectively. In addition, 2-acetoxybutane
attributable to the acetoxylation of the raw material was produced
in 2.40 area %, and 2-iodinebutane was produced 1.35 area %. The
remainder was composed of n-hexane, the solvent, and methyl acetate
resulting from the reaction.
Examples 21, 23-25
[0118] A reaction was performed in the same manner as in Example
17, except that 0.11 g of sodium tetrafluoroborate as the catalyst
was replaced with: 0.168 g of sodium hexafluorophosphate; 0.062 g
of sodium hydrogen difluoride; 0.119 g of sodium sulfamate, and
0.084 g of sodium hydrogen carbonate. The reaction results are
summarized in Table 1.
Example 22
[0119] A reaction was performed in the same manner as in Example
17, except that 0.11 g of sodium tetrafluoroborate as the catalyst
was replaced with 0.085 g of sodium nitrate, and further the
stirring time at 20.degree. C. was changed to 7 hours. After the
completion of the reaction, the reaction mixture was analyzed by
GC, and consequently it was found that that sec-butyl methyl ether,
the raw material, was substantially disappeared, 2-fluorobutane,
the target compound, was produced in 14.63 area %, and 1-butene,
(E)-2-butene, and (Z)-2-butene were produced in 0.14 area %, 4.73
area %, and 2.02 area %, respectively. In addition, 2-acetoxybutane
attributable to the acetoxylation of the raw material was produced
in 2.58 area %. The remainder was composed of n-hexane, the
solvent, and methyl acetate resulting from the reaction.
Example 26
[0120] A reaction was performed in the same manner as in Example
17, except that 0.11 g of sodium tetrafluoroborate as the catalyst
was replaced with 0.104 g of sodium hydrogen sulfite, and further
the stirring time at 20.degree. C. was changed to 7 hours. After
the completion of the reaction, the reaction mixture was analyzed
by GC, and consequently it was found that that sec-butyl methyl
ether, the raw material, was substantially disappeared,
2-fluorobutane, the target compound, was produced in 14.21 area %,
and 1-butene, (E)-2-butene, and (Z)-2-butene were produced in 0.12
area %, 4.46 area %, and 2.04 area %, respectively. In addition,
2-acetoxybutane attributable to the acetoxylation of the raw
material was produced in 2.36 area %. The remainder was composed of
n-hexane, the solvent, and methyl acetate resulting from the
reaction.
Examples 27-40
[0121] A reaction was performed in the same manner as in Example
17, except that 0.11 g of sodium tetrafluoroborate as the catalyst
was replaced with 0.063 g of sodium sulfite, 0.071 g of sodium
sulfate, 0.053 g of sodium carbonate, 0.055 of sodium phosphate,
0.087 g of sodium thiosulfate, 0.082 g of sodium acetate, 0.068 g
of sodium formate, 0.067 g of sodium oxalate, 0.08 g of sodium
maleate, 0.118 g of sodium methanesulfonate, 0.194 g of sodium
p-toluenesulfonate, 0.136 g of sodium trifluoroacetate, 0.236 g of
sodium heptafluorobutyrate, and 0.172 g of sodium
trifluoromethanesulfonate. The reaction results are summarized in
Table 1.
Example 41
[0122] A reaction was performed in the same manner as in Example
17, except that n-hexane as the solvent was changed to n-heptane.
After the completion of the reaction, the reaction mixture was
analyzed by GC, and consequently it was found that that sec-butyl
methyl ether, the raw material, was substantially disappeared,
2-fluorobutane, the target compound, was produced in 9.57 area %,
and 1-butene, (E)-2-butene, and (Z)-2-butene were produced in 0.13
area %, 5.82 area %, and 2.13 area %, respectively. In addition,
2-acetoxybutane attributable to the acetoxylation of the raw
material was produced in 2.55 area %. The remainder was composed of
n-heptane, the solvent, and methyl acetate resulting from the
reaction.
Example 42
[0123] A reaction was performed in the same manner as in Example
17, except that n-hexane as the solvent was changed to cyclohexane.
After the completion of the reaction, the reaction mixture was
analyzed by GC, and consequently it was found that that sec-butyl
methyl ether, the raw material, was substantially disappeared,
2-fluorobutane, the target compound, was produced in 11.75 area %,
and 1-butene, (E)-2-butene, and (Z)-2-butene were produced in 0.15
area %, 6.36 area %, and 2.18 area %, respectively. In addition,
2-acetoxybutane attributable to the acetoxylation of the raw
material was produced in 2.01 area %. The remainder was composed of
cyclohexane, the solvent, and methyl acetate resulting from the
reaction.
Example 43
[0124] A reaction was performed in the same manner as in Example
17, except that 2.48 g of acetyl fluoride was changed to 3.04 g
propionyl fluoride synthesized in Production Example 5. After the
completion of the reaction, the reaction mixture was analyzed by
GC, and consequently it was found that that sec-butyl methyl ether,
the raw material, was substantially disappeared, 2-fluorobutane,
the target compound, was produced in 8.21 area %, and 1-butene,
(E)-2-butene, and (Z)-2-butene were produced in 0.14 area %, 6.43
area %, and 2.17 area %, respectively. In addition,
2-propionyloxybutane attributable to the propionyloxylation of the
raw material was produced in 3.98 area %. The remainder was
composed of n-hexane, the solvent, and methyl propionate resulting
from the reaction.
Example 44
[0125] A reaction was performed in the same manner as in Example
17, except that 1.76 g of sec-butyl methyl ether as the raw
material was changed to 2.04 g of sec-pentyl methyl ether, and
n-hexane as the solvent was changed to n-heptane. After the
completion of the reaction, the reaction mixture was analyzed by
GC, and consequently it was found that that 2-pentyl methyl ether,
the raw material, was disappeared, 2-fluoropentane, the target
compound, was produced in 9.34 area %, and 3-fluoropentane was
produced in 4.47 area % and pentene as an isomer mixture was
produced in 8.28 area %. In addition, 2-acetoxypentane attributable
to the acetoxylation of the raw material was produced in 2.34 area
%.
Example 45
[0126] A reaction was performed in the same manner as in Example
17, except that 1.76 g of sec-butyl methyl ether as the raw
material was changed to 2.04 g of sec-butyl ethyl ether synthesized
in Production Example 2. After the completion of the reaction, the
reaction mixture was analyzed by GC, and consequently it was found
that sec-butyl ethyl ether, the raw material, was substantially
disappeared, 2-fluorobutane, the target compound, was produced in
11.04 area %, and 1-butene, (E)-2-butene, and (Z)-2-butene were
produced in 0.12 area %, 3.82 area %, and 1.31 area %,
respectively. In addition, 2-acetoxybutane attributable to the
acetoxylation of the raw material was produced only in 3.52 area
%.
Example 46
[0127] A reaction was performed in the same manner as in Example
17, except that 1.76 g of sec-butyl methyl ether as the raw
material was changed to 1.76 g of t-butyl methyl ether. After the
completion of the reaction, the reaction mixture was analyzed by
GC, and consequently it was found that t-butyl methyl ether, the
raw material, remained in 1.34 area %, t-butyl fluoride, the target
compound, was produced in 15.11 area %, and isobutene in 1.58 area
%. In addition, t-butyl acetate attributable to the acetoxylation
of the raw material was produced only in 1.93 area %.
Example 47
[0128] A reaction was performed in the same manner as in Example
17, except that 1.76 g of sec-butyl methyl ether as the raw
material was changed to 2.04 g of t-butyl ethyl ether. After the
completion of the reaction, the reaction mixture was analyzed by
GC, and consequently it was found that t-butyl ethyl ether, the raw
material, was substantially disappeared, t-butyl fluoride, the
target compound, was produced in 17.96 area %, and isobutene in
1.45 area %. In addition, t-butyl acetate attributable to the
acetoxylation of the raw material was produced in 1.48 area %.
Comparative Example 1
[0129] In a 50 mL volume glass reactor equipped with a stirring bar
and a Dimroth condenser, 3.52 g of sec-butyl methyl ether
synthesized in Production Example 1, 2.98 g of acetyl fluoride
synthesized in Production Example 4, and 10 mL of n-hexane were
charged, and the resulting mixture was cooled to 0.degree. C. and
the content was stirred. To the cooled mixture, 2.48 g of boron
trifluoride tetrahydrofuran complex was added by means of a
syringe, and the resulting mixture was stirred for 3 hours while
being held at 0.degree. C.
[0130] The content was analyzed by GC, and consequently it was
found that sec-butyl methyl ether, the raw material, was
substantially disappeared, 2-fluorobutane, the target compound, was
produced in 24.45 area %, and 1-butene, (E)-2-butene, and
(Z)-2-butene were produced in 0.18 area %, 6.50 area %, and 2.00
area %, respectively. In addition, 2-acetoxybutane attributable to
the acetoxylation of the raw material was produced in 0.35 area %.
The remainder was composed of n-hexane, the solvent, and
tetrahydrofuran derived from the complex, and methyl acetate. The
reaction liquid was dark brown.
[0131] The results of Examples 1-47 and Comparative Example 1 are
summarized in Table 1 below.
[0132] In Table 1, Ts represents 4-methylphenylsulfonyl.
TABLE-US-00001 TABLE 1 Ether Acid Reaction Compound Fluoride Time
(1) (2) Catalyst Solvent (h) Example 1 sec-butyl acetyl LiBF.sub.4
n-hexane 7 methyl ether fluoride Example 2 sec-butyl acetyl LiF
n-hexane 7 methyl ether fluoride Example 3 sec-butyl acetyl LiCl
n-hexane 7 methyl ether fluoride Example 4 sec-butyl acetyl LiBr
n-hexane 7 methyl ether fluoride Example 5 sec-butyl acetyl LiI
n-hexane 7 methyl ether fluoride Example 6 sec-butyl acetyl
LiNO.sub.3 n-hexane 7.5 methyl ether fluoride Example 7 sec-butyl
acetyl Li.sub.2CO.sub.3 n-hexane 7 methyl ether fluoride Example 8
sec-butyl acetyl Li.sub.3PO.sub.4 n-hexane 7 methyl ether fluoride
Example 9 sec-butyl acetyl H.sub.2NSO.sub.3Li n-hexane 7 methyl
ether fluoride Example 10 sec-butyl acetyl CH.sub.3CO.sub.2Li
n-hexane 7 methyl ether fluoride Example 11 sec-butyl acetyl
LiO.sub.2CC.dbd.CCO.sub.2Li n-hexane 7 methyl ether fluoride
Example 12 sec-butyl acetyl (CO.sub.2Li).sub.2 n-hexane 7 methyl
ether fluoride Example 13 sec-butyl acetyl CH.sub.3SO.sub.3Li
n-hexane 7 methyl ether fluoride Example 14 sec-butyl acetyl TsOLi
n-hexane 7 methyl ether fluoride Example 15 sec-butyl acetyl
CF.sub.3SO.sub.3Li n-hexane 8 methyl ether fluoride Example 16
sec-butyl acetyl C.sub.4F.sub.9SO.sub.3Li n-hexane 7 methyl ether
fluoride Example 17 sec-butyl acetyl NaBF.sub.4 n-hexane 7 methyl
ether fluoride Example 18 sec-butyl acetyl NaF n-hexane 7 methyl
ether fluoride Example 19 sec-butyl acetyl NaBr n-hexane 7 methyl
ether fluoride Example 20 sec-butyl acetyl NaI n-hexane 6 methyl
ether fluoride Example 21 sec-butyl acetyl NaPF.sub.6 n-hexane 7
methyl ether fluoride Example 22 sec-butyl acetyl NaNO.sub.3
n-hexane 7.5 methyl ether fluoride Example 23 sec-butyl acetyl
NaHF.sub.2 n-hexane 7 methyl ether fluoride Example 24 sec-butyl
acetyl H.sub.2NSO.sub.3Na n-hexane 7 methyl ether fluoride Example
25 sec-butyl acetyl NaHCO.sub.3 n-hexane 7 methyl ether fluoride
Example 26 sec-butyl acetyl NaHSO.sub.3 n-hexane 7.5 methyl ether
fluoride Example 27 sec-butyl acetyl Na.sub.2SO.sub.3 n-hexane 7
methyl ether fluoride Example 28 sec-butyl acetyl Na.sub.2SO.sub.4
n-hexane 7 methyl ether fluoride Example 29 sec-butyl acetyl
Na.sub.2CO.sub.3 n-hexane 7 methyl ether fluoride Example 30
sec-butyl acetyl Na.sub.3PO.sub.4 n-hexane 7 methyl ether fluoride
Example 31 sec-butyl acetyl Na.sub.2S.sub.2O.sub.4 n-hexane 7
methyl ether fluoride Example 32 sec-butyl acetyl
CH.sub.3CO.sub.2Na n-hexane 7 methyl ether fluoride Example 33
sec-butyl acetyl HCO.sub.2Na n-hexane 7 methyl ether fluoride
Example 34 sec-butyl acetyl (CO.sub.2Na).sub.2 n-hexane 7 methyl
ether fluoride Example 35 sec-butyl acetyl
NaO.sub.2CC.dbd.CCO.sub.2Na n-hexane 7 methyl ether fluoride
Example 36 sec-butyl acetyl CH.sub.3SO.sub.3Na n-hexane 7 methyl
ether fluoride Example 37 sec-butyl acetyl TsONa n-hexane 7 methyl
ether fluoride Example 38 sec-butyl acetyl CF.sub.3CO.sub.2Na
n-hexane 7 methyl ether fluoride Example 39 sec-butyl acetyl
C.sub.3F.sub.7CO.sub.2Na n-hexane 7 methyl ether fluoride Example
40 sec-butyl acetyl CF.sub.3SO.sub.3Na n-hexane 7 methyl ether
fluoride Example 41 sec-butyl acetyl NaBF.sub.4 n-heptane 7 methyl
ether fluoride Example 42 sec-butyl acetyl NaBF.sub.4 cyclohexane 7
methyl ether fluoride Example 43 sec-butyl propionyl NaBF.sub.4
n-hexane 7 methyl ether fluoride Example 44 2-pentyl acetyl
NaBF.sub.4 n-heptane 7 methyl ether fluoride Example 45 sec-butyl
acetyl NaBF.sub.4 n-hexane 7 methyl ether fluoride Example 46
t-butyl acetyl NaBF.sub.4 n-hexane 7 methyl ether fluoride Example
47 t-butyl acetyl NaBF.sub.4 n-hexane 7 methyl ether fluoride
Comparative sec-butyl acetyl BF.sub.3.cndot.THF n-hexane 3 Exampple
1 methyl ether fluoride Product (area %) Raw Material- 1- (E)-2
(Z)-2- 3-Fluoro Derived Halogen Raw Target Butene Butene Butene
Pentane Pentene Isobutene Component Exchanger Material Example 1
8.87 0.14 4.22 2.71 3.84 .apprxeq.0 Example 2 16.73 0.12 4.69 1.96
2.00 .apprxeq.0 Example 3 13.12 0.11 4.09 1.82 2.31 .apprxeq.0
Example 4 12.26 0.14 4.71 2.25 3.21 0.15 .apprxeq.0 Example 5 12.98
0.18 5.01 2.23 2.33 1.18 .apprxeq.0 Example 6 15.03 0.11 4.40 1.77
2.36 1.41 Example 7 12.64 0.15 5.55 2.23 2.94 .apprxeq.0 Example 8
15.02 0.14 4.96 2.13 1.56 .apprxeq.0 Example 9 14.18 0.13 4.39 1.99
2.32 .apprxeq.0 Example 10 13.06 0.11 4.15 1.88 2.95 .apprxeq.0
Example 11 16.54 0.14 4.83 2.05 2.23 .apprxeq.0 Example 12 11.57
0.09 3.56 1.57 2.09 3.35 Example 13 14.54 0.18 6.26 2.70 1.97
.apprxeq.0 Example 14 13.68 0.11 4.09 1.76 2.79 1.63 Example 15
10.76 0.28 7.54 3.29 2.61 2.09 Example 16 12.93 0.23 6.46 2.90 2.64
.apprxeq.0 Example 17 12.61 0.13 5.62 1.95 2.25 .apprxeq.0 Example
18 15.23 0.18 6.27 2.29 2.17 1.79 Example 19 12.83 0.13 4.79 2.08
2.88 .apprxeq.0 Example 20 13.34 0.21 5.72 2.29 2.40 1.35
.apprxeq.0 Example 21 8.83 0.25 6.34 3.59 2.73 .apprxeq.0 Example
22 14.63 0.14 4.73 2.02 2.58 .apprxeq.0 Example 23 13.28 0.11 4.16
1.89 2.81 1.17 Example 24 16.14 0.17 5.30 2.29 1.89 1.81 Example 25
13.25 0.15 5.26 1.84 2.76 2.71 Example 26 14.21 0.12 4.46 2.04 2.36
.apprxeq.0 Example 27 14.02 0.16 5.35 2.22 1.96 .apprxeq.0 Example
28 13.32 0.18 6.04 2.32 2.53 .apprxeq.0 Example 29 14.12 0.11 4.23
1.93 2.39 .apprxeq.0 Example 30 13.95 0.10 3.78 1.67 1.97 1.75
Example 31 13.22 0.11 3.72 1.61 1.67 4.73 Example 32 14.30 0.15
5.06 2.22 2.05 .apprxeq.0 Example 33 11.05 0.08 2.77 1.13 1.42 8.99
Example 34 11.60 0.09 3.33 1.33 1.36 7.98 Example 35 13.61 0.17
5.60 2.56 2.60 .apprxeq.0 Example 36 12.49 0.12 4.40 1.89 2.41 1.49
Example 37 11.43 0.10 3.53 1.46 1.70 5.57 Example 38 12.16 0.13
5.24 2.06 2.88 .apprxeq.0 Example 39 13.47 0.11 4.08 1.69 1.74 3.45
Example 40 12.99 0.17 5.21 2.52 2.81 .apprxeq.0 Example 41 9.57
0.13 5.82 2.13 2.55 .apprxeq.0 Example 42 11.75 0.15 6.36 2.18 2.01
.apprxeq.0 Example 43 8.21 0.14 6.43 2.17 3.98 .apprxeq.0 Example
44 9.34 4.47 8.28 2.34 .apprxeq.0 Example 45 11.04 0.12 3.82 1.31
3.52 .apprxeq.0 Example 46 15.11 1.58 1.93 1.34 Example 47 17.96
1.45 1.48 .apprxeq.0 Comparative 24.45 0.18 6.50 2.00 0.35
.apprxeq.0 Exampple 1
[0133] The followings can be found from the aforementioned
results.
[0134] In Examples where lithium salt or sodium salt was used as
the catalyst, no ether compound is by-produced, the catalyst
residue is removable through mere filtering after the reaction, and
a substantially colorless reaction liquid is recovered.
[0135] On the other hand, in Comparative Example 1 where boron
trifluoride tetrahydrofuran complex was used as the catalyst,
tetrahydrofuran (ether compound (impurities)) liberated from the
catalyst remains in the reaction liquid. The removal of boron
trifluoride tetrahydrofuran complex, which is a liquid, requires
post-treatment operation such as neutralization after the
completion of reaction, which makes the operation cumbersome.
Further, the reaction liquid thus obtained was dark-browned.
[0136] According to the disclosed method, the resulting reaction
liquid is substantially colorless, and the post-treatment after the
reaction is simple, which allows for industrially advantageous
manufacture of fluorinated hydrocarbon such as 2-fluorobutane.
* * * * *